GSJ: Volume 8, Issue 8, August 2020, Online: ISSN 2320-9186...Heterocyclic Functional & related...

GSJ: Volume 8, Issue 8, August 2020, Online: ISSN 2320-9186

www.globalscientificjournal.com Aqueous & Microwave Synthesis & Spectral Behaviour of Some Selected

Photosensitizer Zero-Methine & Self-Assembly Mero Cyanine Dyes

Ahmed. I. M. Koraiema, Reda M. Abel Aal b& Islam. M. S. Abdellaha aChemistry Department, Faculty of Science, Aswan University, Aswan, Egypt

bChemistry Department, Faculty of Science, Sues University, Sues, Egypt ABSTRACT Aqueous Synthesis (water mediated) of three components Reactions resulted in dipyrazolo

[3,4-b: 4',3'-e]pyridin-4-yl-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one and 5-(3-methyl-5-oxo-1-

phenyl-4,5-di[H]-1H-pyrazol-4-yl)-9,10-di[H]pyrido[2,3-d:6,5-d']dipyrimidine-2,4,6,8(1H,3H,5

H,7H)-tetra-one (25, 26)A. Thermal piperidine catalysis of the later (25, 26)A afforded bis-

pyrazolo[3,4-b:4',3'-e] pyridin-4(1H, 7H, 8H)-pyrido [2, 3-d:6, 5-d'] dipyrimidine self-assembly

[ICT]functional mero cyanine dyes (25, 26)B pyrazolo[3,4-b] pyridin-zero-5(4)-methine

cyanine (28a, b) & related pyrazolo[3,4-b]pyridin-(7H)-zero(mono)-5[4(1)]-4-[2(4)]methine

cyanine dyes (29a-d) were synthesised via acetic anhydride microwave irradiation of

heterocyclization process of N-Ethyl-4-(2-(5-imino-3-methyl-1-phenyl-4,5-di[H]-1H-pyrazol-

4-yl)-2-keto-methylene-pyridin(quinolin)-1-ium (27a,b)flowingly interacted with 2-methyl-

pyridin (quinolin)-2(4)-ium ethiodide salts under piperidine catalysis. Spiro [pyrazolo [3, 4-b]

pyridin-4, 9'-xanthen]-N-ethyl-pyridin (quinolin)-zero (mono)-5(4)[15(4(1))] methine cyanine

dyes were synthesised.to improve the specific characterization, photosensitization

behaviour. The heterocyclic functional & related cyanine dyes were identified by elemental &

spectral analyses. Special attention has been focus on absorption (emission) spectral,

(media) chromic behaviour (acid-base properties).

Keywords: Recent Methodology, Aqueous Synthesis & Microwave synthesis, Absorption

(Emission) Spectral, Solvato (Media) Chromic Behaviour

GSJ: Volume 8, Issue 8, August 2020 ISSN 2320-9186 1355

GSJ© 2020 www.globalscientificjournal.com

http://www.globalscientificjournal.com/

Graphical Abstract

AcONH4

oxalic acid (20 mol%)Water

Reflux (60-80 min)

NN

CHO

O

Ph

NH

NH

O

O

NH

HN

NH

O

O

NNO

Ph

NNPh

O

NN

PhNH

NN

Ph

NNPh

OAcONH4


Reflux (60-80 min)

(25A)(26A)

NH

NH

O

O

O2Mol.

2Mol.

(1)

(27a, b) (28a, b)

NN NH

Ph

O

NI

NN N

HPh

O NI

Ac2O, 110°C AA

(28a, b) (30a, b)

NN N

Ph

N

I

O OHHO

H+/sand bath

H

OHHO

Bimolecular ratioN

N NHPh

O

N

I

AA

Synthetic Routes of Starting Precursors

INTRODUCTION Special attention was given to an implementation, preparations and Spectral Behaviour of

heterocyclic cyanine to show the various aspects in order to satisfy the great demand in

industrial and various biological fields. There was growing interest in the synthesis of

heterocyclic compounds in view of their use in the cyanine dyes synthesis [1-4]. Mero

cyanine dyes had a large application as analytical reagents over a wide pH range this back

to cyanine dyes had a permanent cationic charge in the basic media which then discharged

on acidification [5]. Mero cyanine was first synthesized from a century ago and continued to

now days [6-9] but few of them focus on the synthesis of N-bridgehead mero cyanine dyes

[10-12]. Greener Synthesis of Heterocycles in Water Mediated Condition Technic of Some

Selected Self-Assembly [ICT] Heterocyclic Functional & related methine cyanine dyes had

been conducted by using of environmentally benign water as a solvent supports the green

aspect of method as a simple and convenient one step method for synthesis of some

heterocyclic compounds were reported and the major advantages of the proposed method

were its simplicity, short reaction time, easy work-up, inexpensive catalyst, and good yields.

[13-20]. Aqueous synthesis is a simple & convenient one step method for synthesis of

heterocyclic moieties & related methine cyanine dyes. Such new water reaction medium

catalysis was reported & provides several advantages such as good yields, cheap catalyst,

short reaction time, easy work-up, simplicity in operation & a rapid, high yielding. The use of

environmentally benign water as a solvent supports the green aspect of method and



significant advancement toward an environmentally friendly reaction [21]. New methodology

(aqueous synthesis) was conducted for self-assembly [ICT] functional & related methine

cyanine dyes synthesis [29, 30]. Thus, one pot synthesis of three component reaction under

aqueous synthesis achieved the green aspect of the process.

RESULTS AND DISCUSSION Interaction of an ethanolic solution of 4-formyl-3-methyl-1-phenyl-pyrazolin-5-one (1), equimolar ratio, [22; 23] and 3-methyl-1-phenyl-1H-pyrazolin-5-one and/or barbituric acid, in

bimolecular ratio & ammonium acetate in aqueous solution of oxalic acid afforded 4-(3,5-

dimethyl-1,7-diphenyl-1,4,7,8-tetra[H]dipyrazolo[3,4-b:4',3'-e]pyridin-4-yl)-3-methyl-1-phenyl-

1H-pyrazol-5(4H)-one & 5-(3-methyl-5-oxo-1-phenyl-4,5-di[H]-1H-pyrazol-4-yl)-9,10-di[H]

pyrido[2,3-d:6,5-d'] dipyrimidin-2,4,6,8(1H,3H,5H,7H)-tetra-one (25,26)A, respectively,. Thermal piperidine catalysis flowingly 4-(3,5-dimethyl-1, 7-diphenyl-1, 4, 7, 8-tetra[H]di-

pyrazolo[3, 4-b:4', 3'-e] pyridin-4-yl)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one and 5-(3-

methyl-5-oxo-1-phenyl-4, 5-di[H]-1H-pyrazol-4-yl)-9, 10-di[H] pyrido [2,3-d:6,5-d']dipyrimidin-

2, 4, 6, 8(1H, 3H, 5H, 7H)-tetra-one (25A, 26A) flowingly an ethanol extraction afforded 4-

(3,5-dimethyl-1,7-diphenyl-bis-pyrazolo[3,4-b:4',3'-e] pyridin-4(1H, 7H, 8H)-pyrido [2, 3-d:6,

5-d'] dipyrimidine self-assembly endocyclic [ICT] functional mero cyanine dyes (25, 26)B. An

eye-opening feat of building up pyrazolo [3,4-b]pyridin-zero(mono) was synthesized. Thus,

acetic anhydride catalysis of 3-methyl-1-phenyl-pyrazolin-5-imine-4-keto-methylene-N-

pyridin (quinolin)-4-ium-iodide) (27a,b) [29;33] undergoes molecular heterocyclization to

afford 3,6-dimethyl-4-oxo-1-phenyl-4,7-di[H]-1H-pyrazolo[3,4-b]pyridin- zero-5(4)-methine

cyanine (28a, b). The interaction of an ethanolic solution of (28a, b) and 2(4)-methyl-pyridin

(quinolin)-[2(4)]ethiodide salt, in equimolar ratio, under piperidine catalysis afforded 3-

methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin-(7H)-zero(mono)-5[4(1)]-4-[2(4)]methine cyanine

dyes (29a-d). Acetic anhydride catalysis of 3-methyl-1-phenyl-pyrazolin-5-imine-4-keto-

methylene-N-pyridin(quinolin)-4-ium-iodide)(27a,b),[29,30]undergoes molecular hetero-

cyclization under irradiation in microwave oven (appropriate time at 200 watt) afforded 3,6-

dimethyl-4-oxo-1-phenyl-4,7-di[H]-1H-pyrazolo[3,4-b]pyridin-zero-5(4)-methine cyanine (28a,b). The interaction of an ethanolic solution of (28a, b) & 2(4)-methyl-pyridin(quinolin)-

[2(4)] ethiodide salt, equimolar ratio, under piperidine catalysis afforded 3-methyl-1-phenyl-

1H-pyrazolo[3,4-b]pyridin-(7H)-zero (mono)-5[4(1)]-4-[2(4)]methine cyanine dyes (29a-d), Scheme (1). In continuation of our work, methine cyanine synthesis of 1-ethyl-4-(3-methyl-5-

oxo-1-phenyl-1,5-di[H]spiro[pyrazole-4,3'-pyrrolo[3',4':3,4]pyrazolo[1,5-a]pyridin]-mono-1[4(

1)] & 4-(5-(acetyl-imino)-1',3-dimethyl-1-phenyl-1,5-di[H] spiro [pyrazol-4,3'-pyrrolo [3, 4-

a]indolizin]-zero[4(1)]methine cyanine dyes (31a,b, (32,33)a-c were synthesised via an

ethanolic solution of 3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin(quinolin)-4(7H)-one-5-

zero-[4(1)] methine (28a, b) & resorcinol, equi (bi) molar ratios, under acidic medium



undergoes cyclocondensation reaction flowingly cyclo-dehydration processes to afford 3',6'-

dihydroxy-3,6-dimethyl-1-phenyl-1,7-di-[H]spiro[pyrazolo[3,4-b]pyridin-4,9'-xanthen]-zero-

5[4(1)] methine cyanines (30a, b). Selective quaternization of an ethanolic solution of (30a, b), equimolar ratio, using excess ethyl iodide afforded 3',6'-dihydroxy-3,6-dimethyl-1-phenyl-

1,7-di[H]spiro[pyrazolo[3,4-b]pyridine-4,9'-xanthen]-2-ium-ethiodide-zero-5[4(1)]methine

cyanine (31a, b). The interaction of an ethanolic solution of (31a, b) & pyridin (quinolin)-4(1)-

ium-ethiodide salts ,equimolar ratio, under piperidine catalysis afforded 3', 6'-dihydroxy-3,6-

dimethyl-1-phenyl-1,7-di[H]spiro[pyrazolo[3,4-b]pyridin-4,9'-xanthen]-N-ethyl-pyridin

(quinolin)-zero[mono]-5(4) [15 (4(1)) ]methine cyanine dyes (32, 33)a-c, Scheme (2).

AcONH4


Reflux (60-80 min)

NN

CHO

O

Ph

NH

NH

O

O

NH

HN

NH

O

O

NNO

PhNNPh

O

NN

PhNH

NN

Ph

NNPh

O

AcONH4


Reflux (60-80 min)

(25A) (26A)

NH

NH

O

O

O

2Mol.2Mol.

(1)

(25B)

NH

NH

O

O

NH

HN

NH

O

O

NNO

Ph

NN

PhNH

NN

Ph

NNPh

O

EtOH/Pip.

(26B)

EtOH/Pip.

(27a, b) (28a, b)

(29a-d)

NN NH

Ph

O

NI

NN N

HPh

O NI

NN N

Ph

N

I

N

I

Ac2O, 110°CEtOH, Pip.

H

A

A

A

B

NI

B

MW/ H+

Scheme (1) Substituents: (27, 28)a, b: A=H-4-ium (a) A=C4H4-4-ium (b); (29a-d): A(B)=H-4-ium (C4H4-2-ium) (a);

A(B)=H-4-ium (H-4-ium) (b); A(B)=C4H4-4-ium (C4H4-2-ium) (c); A(B)=C4H4-4-ium (H-4-ium)

(d)



(28a, b)(30a, b)

NN

N

Ph

NI

O

HO

HO

(31a, b)

NN

N

Ph

N I

O

HO

HO I

(32, 33)a-c

NN

N

Ph

O

HO

HO

NI

H+/sand bath

EtI, 60°CH H

H

A

A

EtOH, Pip.

NI

AOHHO

Bimolecular ratio

N I

A`

NN

NH

Ph

O

N IA

A

Scheme (2) Substituents

(28, 30) a, b: A=H-4-ium (a), C4H4-4(1)-ium (b), (31, 32) a-c: A=H-4-ium (a); A=C4H4-4-ium

(b); A= H-4-ium (c).

The formation of (25, 26)A was suggested to proceed via bimolecular nucleophilic addition

reaction of 3-methyl-1-phenyl-pyrazolin-5-(one) and/or barbituric acid to formyl group of 4-

formyl-3-methyl-1-phenyl-pyrazolin-5-one to form an intermediate (A, A`) flowingly an

enolization to give an intermediate (B, B`). The later intermediates (B, B`) undergo

heterocyclization process under ammonium acetate to give desire (25, 26)A Equation (1)

NN

CHO

O

Ph

NNPh

O


(25A)

(1)

NNPh

O

+HH

NN

Ph

NN

Ph

NNPh

O

O O

AcONH4

NN

Ph

NN

Ph

NNPh

O

OH HO(A)

(B)

NN

PhNH

NN

Ph

NNPh

O

NN

CHO

O

Ph


(26A)

(1)+

NNPh

O

AcONH4

(A`)NH

NNPh

O

NH

NHHN

NH

O

O

O O

O

O

NH

NH

O

O

O

HN

NH

O

O

O

NNPh

O

(B`)

NH

NH

O

O

HO

HN

NH

O

O

OHNH

NHHN

NH

O O

OO

Equation (1): Suggested Formation Mechanism of (25, 26) A

The structure of (25A & 26A) was confirmed by elemental & spectral analysis. IR (νKBr cm-1)

showed, in addition to, general frequency absorption bands at: 3306 cm-1 (γ NH cyclic

pyridine), 3067 & 2926 cm-1 (γ CH, CH3), 1713 cm-1 (γ cyclic C=O), 1594 cm-1 (γ C=C conj.

Ar.), 757 cm-1 (γ phenyl mono-subs.) for (25A); 3313 cm-1 (γ NH cyclic pyridine and

pyrimidine), 3067 & 2926 cm-1 (γ CH, CH3), 1668 cm-1 (γ cyclic C=O), 1542 cm-1 (γ C=C Ar.),

751 cm-1 (γ phenyl mono-subs) for (26A), absorption bands at 3325 cm-1 (γ cyclic pyridine-

NH), 2925 cm-1 (γ CH, CH3), 1663 cm-1 (γ cyclic pyrazole C=O), 1595 cm-1 (γ conj. C=C Ar.),

756 cm-1 (γ phenyl mono-subs.) for (25B) and 3314 cm-1 (γ NH), 3061 cm-1 (γ CH, CH3),

1686 cm-1 (γ C=O), 1594 cm-1 (γ C=C Ar.), 755 cm-1 (γ phenyl mono-subs.) for (26B),

[24,25]. IR (νKBr cm-1) of (30a, b) showed, in addition to, general frequency absorption bands

at 3214 cm-1 (γ OH, xanthene), 2966 cm-1 (CH, heterocyclic quaternary salt), 2928 cm-1 (γ



CH, CH3), 1601 cm-1 (γ C=C conj. Ar), 1499 cm-1 (γ cyclic C=N), 758 cm-1 (γ phenyl mono-

subs.) for (30a) and 3258 cm-1 (γ OH for xanthene), 2968 cm-1 (γ CH, heterocyclic

quaternary salt), 2933 cm-1 (γ CH, CH3), 1597 cm-1 (γ C=C conj.), 1500 cm-1 (γ cyclic C=N),

757 cm-1 (γ Ph mono subs) for (30b), [24,25]. 1H-NMR (DMSO-d6, 500 MHz) spectra of (30a) showed, in addition to, general signals at

observed [found]: δ 7.62-7.58 ppm [δ 9.14-7.80 ppm, ∆δ=0.22-1.52 ppm](m, 5H, ph), δ 7.36-

6.57 ppm [δ 7.42 -6.82 ppm, ∆δ=0.06-0.25 ppm] (m, 10H, Ar), δ 4 ppm [ δ 4.57 ppm,

∆δ=0.57 ppm] (s, 1H, NH), δ 5.35 ppm [δ 4.53 ppm, ∆δ=0.82 ppm] (s, 2H, 2OH), δ 4.07

ppm[ δ 3.25 ppm, ∆δ=0.82 ppm](q, 2H, CH2), δ 2.26-1.93 ppm[ δ 2.37- 2.14 ppm, ∆δ=0.11-

0.21 ppm] (s, 6H, 2CH3), δ 1.41 ppm[δ 1.53 ppm, ∆δ=0.12] (t, 3H, CH3), [26,27]. 1HNMR

(DMSO-d6, 500 MHz) spectra of (25A, 26A) showed, in addition to, general signals at

observed [found]: δ 7.94-7.43 ppm [δ 7.94 –7.28 ppm, ∆ δ=0.15 ppm (m, 15H, 3Ph)], δ 4

ppm [δ 5.45 ppm, ∆δ=1.45 ppm] (s, 1H, cyclic NH)], δ 4.3-3.2 ppm [ δ 4.56 ppm, ∆δ=0.26

ppm] (d, 2H, CH cyclic), δ 1.94-1.93 ppm [δ 2.43-2.12 ppm, ∆δ=0.49 ppm] (s, 9H, 3CH3] for

(25A) [26 & 27]. 1H-NMR spectra of (29a) showed, in addition to, general signals at

observed [found]: δ 7.62-7.45 ppm [δ, 9.90–7.91 ppm, ∆δ=0.46-2.28 ppm] (m, 5H, Ph)], δ

8.81-7.57 ppm [ δ 7.92–6.30 ppm, ∆δ=0.89-1.15 ppm] (m, 10H, 2Ar)], δ 7.15 ppm [δ 5.94,

∆δ=1.21 ppm] (s, 1H,=CH)], δ 4 ppm [δ 5.52 ppm, ∆δ=1.52 ppm] (s, 1H, NH), δ 4.51-4.43

ppm [δ 5.07-4.51 ppm, ∆δ=0.57-0.08 ppm] (q, 4H, 2CH2)], δ 2.47-1.63 ppm [δ 2.74-2.12

ppm, ∆δ=0.27-0.94 ppm] (s, 6H, 2CH3), δ 1.58-1.29 ppm [δ 1.52, ∆δ=0.0.6-0.23 ppm) (t, 6H,

2CH3)] for (29a), [26,27]. Structure of (25, 26)B based on (ESI-Ft-mass) was considered

most likely and in agreement with molecular formula (C31H25N7O), resulted in m/z

found=511.58453 (calcd. 511.58352 For [M]+) with an error ΔM=2.799 ppm for (25B). Molecular formula (C14H8IN3O4) resulted in m/z found =409.14233 (calcd. 409.14367 For [M]

+) with an error of ΔM=2.23 ppm for (26B). Mass spectra 70 ev (m/z) of (30a) based on mass

spectra was considered most likely & in agreement with molecular formula C33H29IN4O3

resulted, in addition to, general abundance peaks at general observed abundance peaks

m/z= 658, 620, 591, 535, 512,213, 91, characteristic abundance molecular ion peaks (base

peak) observes m/z [M+] found m/z=357 (91), [33,34]. [33, 34]. COLOUR AND SPECTRAL BEHAVIOUR

4-(3,5-Dimethyl-1,7-diphenyl-1,4,7,8-tetra[H]dipyrazolo[3,4-b: 4',3'-e] pyridin-4-yl)-3-

methyl-1-phenyl-1H-pyrazol-5(4H)-one & 5-(3-methyl-5-oxo-1-phenyl-4,5-di[H]-1H-

pyrazol-4-yl)-9,10-di[H]pyrido[2,3-d:6,5-d']dipyrimidin-2,4,6,8 (1H, 3H,5H,7H)-tetra-

one (25, 26) A &4-(3,5-dimethyl-1,7-diphenyl-bis-pyrazolo[3,4-b:4',3'-e]pyridin-

4(1H,7H,8H)-pyrido[2,3-d:6,5-d']di-pyrimidin-self-assembly endo-cyclic [ICT] functional mero cyanine dyes (25, 26)B are highly colour compounds. Their colour in



an ethanolic solution are ranging from pale brown to red (reddish brown to red),

easily soluble in either polar or non-polar exhibiting colour solutions (violet), they are

soluble in conc. H2SO4 exhibit no iodine vapour on warming, Tables (8). 3-Methyl-1-

phenyl-1H-pyrazolo[3,4-b]pyridin-(7H)-zero(mono)-5[4(1)]-4-[2(4)] methine cyanine

dyes (29a-d) are highly colour compounds their colour are ranging from red to violet

and in an ethanolic solution are ranging from red to violet, easily soluble in either

polar or non-polar exhibiting colored solutions (green blue to green), they are soluble

in conc. H2SO4 exhibit iodine vapour on warming. Such dyes (29a-d) exhibit on

acidification green blue in colour, Tables (1, 2 & 5). 3',6'-Dihydroxy-3,6-dimethyl-1-

phenyl-1,7-di[H]spiro[pyra-zolo[3,4-b]pyridin-4,9'-xanthen]-zero-5[4(1)]methine

(30a,b) & 3', 6'-dihydroxy-3, 6-dimethyl-1-phenyl-1,7-di[H]spiro [pyrazolo [3,4-

b]pyridin-4, 9'-xanthen]-N-ethyl-pyridin (quinolin)-zero (mono)-5(4)[15 (4(1))] methine

cyanine dyes (32, 33)a-c are highly colour compounds. Their colour in an ethanolic

solution are ranging from red brown to red for dyes (30a, b) and red to violet for (32, 33)a-c, they are easily soluble in either polar or non-polar) exhibiting colored

solutions (violet/ blue) for (30a, b) & blue green to orange for (32, 33)a-c, they are

soluble in conc. H2SO4 exhibit iodine vapour on warming. Such dyes (30a, b & (32, 33) a-c exhibit on acidification violet in colour. Meanwhile on basification exhibit

green blue (green) in colour, Tables (2 & 4-6). In point view of spectral behavior of

the absorption (emission) spectra of 4-(3,5-dimethyl-1,7-diphenyl-1,4,7,8-

tetra[H]dipyrazolo [3,4-b:4',3'-e]pyridin-4-yl)-3-methyl-1-phenyl-1H-pyrazolin-5(4H)-

one (25A) and/or 5-(3-methyl-5-oxo-1-phenyl-4,5-di[H]-1H-pyrazol-4-yl)-9,10-

di[H]pyrido[2,3-d:6,5-d']dipyrimidin-2,4,6,8(1H,3H,5H,7H)-tetraone (26A), in 95%

ethanol, the photosensitization resulted in absorption (emission) bands,

batho(hypso) chromically shifted depending on the nature of heterocycle nuclei.

Thus, dyes absorbed fundamental light of violet & emitted (yellow green) in colour as

they have got absorption (emission) values at (25A, 26A; λmax=399, 401 nm;

εmax=21395, 31810 M-1cm-1] (25, 26) A, E max=460, 506 nm]. Meanwhile self-

assembly-4-(3,5-dimethyl-1,7-diphenyl-dipyrazolo[3,4-b:4',3'-e]pyridin-4(1H,7H,8H)-

3-methyl-1-phenyl-1H-pyrazol-5 (4H)-one functional endocyclic mero (25B) & self-

assembly 9, 10-di[H]pyrido[2, 3-d:6, 5-d'] dipyrimidin-2,4,6,8(1,3,5,7[H])-tetraone

functional endo cyclic mero cyanine dye (26B) in 95% ethanol, photosensitization

resulted in absorption (emission) bands, batho(hypso) chromically shifted depending



on nature of heterocycle nuclei. Thus, the dyes absorbed fundamental light of violet

& emitted (yellow green) in colour as they have got absorption (emission) values at

(25B, 26B; λmax=412, 422 nm; εmax=1081, 937 M-1cm-1] (25B, 26B, Emax=118, 120

nm) Table (1). In comparing the absorption spectra of (25B and 26B), It was obvious

that the dye (25B) is hypsochomic shift compared to (26B) attributed to highest

stability of six membered ring (pyrimidine) in (26B) compared to five membered ring

(pyrazole) in (25B), Table (1). The spectral behavior & photosensitization of 3-methyl-1-phenyl-1H-pyrazolo [3,4-b]

pyridin-(7H)-5-zero [4(1)] or mono [2(4)] methine cyanine dyes (29a-d) in 95% EtOH

resulted in absorption (emission) bands, batho (hypso) chromically shifted depending

on inserting heterocyclic quaternary salt and their linkage position. Thus, absorbed

fundamental green blue-green and emitted (red-orange) colour, as they have got

absorption (emission) values at (29a; λmax=493 nm; εmax=16050 M-1cm-1] (29a,

Emax=568 nm (27 kcal/mol)]. Substituting of A=H-4-ium, B=C4H4-2-ium in (29a) by

A=H-4-ium, B=H-4-ium in (29b) causes hypsochromic shift of absorption (emission)

by ∆λmax = 10 nm (∆ Emax=18 nm), as they have a got absorption (emission) values

at (29b); λmax=483 nm; εmax=17880 M-1cm-1] (29b; Emax=550 nm (28 kcal/mol)).

Table (2).This is due to decrease conjugation in pyridin-4-ium in (29b) than quinolin-

2-ium (29a) as electron sink. Substituting of A= H-4-ium, B= H-4-ium in (29b) by

A=C4H4-4-ium, B=C4H4-2-ium (29c) causes bathochromic shift of absorption

(emission) by ∆λmax = 53 nm (∆ Emax=39 nm), as they have a got absorption

(emission) values at (29c; λmax=536 nm; εmax=18071 M-1cm-1) (29c; Emax=589 nm (26

kcal/mol)). This is due to more extended conjugation in quinolin-4(2)-ium than

pyridin-4-ium as electron sink. Substituting of A=C4H4-4-ium, B= C4H4-2-ium in dye

(29c) by A=C4H4-4-ium, B=H-4-ium in dye (29d) causes hypsochromic shift of

absorption (emission) by ∆λmax = 41 nm (∆ E max=30 nm) as they have a got

absorption (emission) values at (29d); λmax=495 nm; εmax=19808 M-1cm-1 [29d; E

max=559 nm (30 kcal/mol)]. This is due to the decrease extended conjugated in

pyridine-4-ium as electron sink. It was obvious that dyes (29a-d) have further stock

shift between fluorescence & emission spectra in 95% ethanol then underwent

change to higher and lower depending on nature of heterocyclic quaternary salt,

thus, dyes (29a-d) showed a range of Δ λ 53-75 nm concomitant with 26-30 x 105

kcal/mol respectively. Such diffuse and large stokes shifts for (29a-d) was suggested



to be partly result of charge transfer (solute-solvent) interaction of such dyes, in

addition to, stokes shift effects the generation properties were explained by change

in the mobility of π-electron in conjugated chromophore of such dyes, Table (1). The

excitation energy (E0-0) of dyes depend basically on type of substituents and nature

of heterocyclic quaternary salt (A) which have a great effect on number of π-

conjugations in fluorophore. Thus, the first (lower) excitation energy (E0-0) of (29a; E0-

0=2.31). A=H-4-yl, B=C4H4-2-ium in dye (29a) by A=H-4-yl, B= H-4-ium in dye (29b) (29b; E0-0=2.37) causes higher value of gap (E0-0). This is due to decreasing

conjugation in dyes (29b) than (29a). Substituting A=H-4-yl, B=H-4-yl in dye (29b) by

A=C4H4-4-ium, B=C4H4-2-ium (29c; E0-0=2.21) causes lower value of gap (E0-0). This

is due to increasing conjugation in dye (29c) compared to (29b). Substituting of

A=quinolin-4-ium, B=quinolin-2-ium in (29c) by quinolin-4-ium, B=pyridin-4-ium in

(29d; E0-0=2.28) causes high value of gap (E0-0). This is due to decreasing

conjugation in (29d) compared to (29c). In point view of spectral behavior of 3-

methyl-1-phenyl-1,7-di[H]spiro[pyrazolo[3,4-b]pyridin(quinolin)-4, 9'-xanthene]-3', 6'-

diol-5-zero-[4(1)]methine (30a, b) in 95% EtOH. photosensitization of such dyes

resulted in absorption (emission) bands, batho (hypso) chromically shifted depending

on inserting heterocyclic quaternary salt and their linkage position thus, absorbed

fundamental light of blue-green (yellow-purple) colour as they have got absorption

(emission) values at (30a ; λmax=428 nm; εmax=10050 M-1cm-1] (30a, Emax=570 nm

(60 kcal/mol)]. Substituting of pyridin-4-ium in dye (30a) by quinolin-4-ium in dye

(30b) causes bathochromic shift of absorption (emission) by ∆λmax = 42 nm (∆

Emax=14 nm), as they have a got absorption (emission) values at (30b; λmax=470 nm;

εmax=10780 M-1cm-1),(30b; Emax=584 nm (55 kcal/mol)], Table (2). This is due to

more extended conjugated in quinolin-4-ium than pyridin-1-ium as electron sink. In

point view of spectral behavior of 2'-ethyl-6'-methyl-1'-phenyl-1',2',3',7'-tetra [H]-10H-

spiro[anthracene-9,4'-pyrazolo[3,4-b]pyridine]-3,6-di-ol-3'-mono-3[4(1)]-5'-zero-[4(1)]

methine cyanine (32, 33 a-c) & photosensitization in 95% EtOH of such dyes

resulted in absorption (emission) bands, batho(hypso) chromically shifted depending

on inserting heterocyclic quaternary salt linkage position. Thus, absorbed

fundamental blue green-orange light and emitted (red-green blue) colour as they

have got absorption (emission) values at (32a; λmax=493 nm; εmax=12550 M-1cm-1),

(32a, Emax=566 nm (60 kcal/mol)]. Substituting of A=H-4-ium in dye (32a) by A=C4H4-



4-ium in dye (32b) causes bathochromic shift of absorption (emission) by ∆λmax = 52

nm (∆Emax=60 nm), as they have got absorption (emission) values at (32b); λmax=545

nm; εmax=16520 M-1cm-1 (32b; E max=626 nm (54 kcal/mol)], Table (1). This is due to

the more extended conjugated in quinolin-4-ium than pyridin-1-ium as electron sink.

Substituting of A=C4H4-4-ium in dye (32b) by A=C4H4-1-ium in dye (32c) causes

hypsochromic shift of absorption (emission) by ∆λmax = 15 nm (∆ E max=21 nm), as

they have a got absorption (emission) values at (32c); λmax=530 nm; εmax=6721 M-

1cm-1 (32c; Emax=605 nm (54 kcal/mol)]. This is due to the decrease extended

conjugation in quinolin-2-ium than quinolin-4-ium as electron sink. In point view of

the spectral behaviour dye (33a) absorbed fundamental light green & emitted purple

as they have got absorption (emission) values at (33a; λmax=503 nm; εmax=12010 M-

1cm-1), (33a; E max=584 nm (55 kcal/mol)]. This is due to the decrease extended

conjugation in quinolin-4-ium as electron sink. Substituting of A=H-4-ium in dye in

(33a) by A=C4H4-4-ium (33b) causes bathochromic shift of absorption (emission) by

∆λmax = 95 nm (∆ E max=69 nm) as they have got absorption (emission) values at

(33b; λmax=598 nm; εmax=16430 M-1cm-1) (33b; E max=653 nm (61 kcal/mol)]. This is

due to the increase extended conjugation in two quinolin-4-ium units as electron

sink. Substituting of A=C4H4-4-ium in (33b) by A=C4H4-1-ium (33c) causes

hypsochromic shift of absorption (emission) by ∆λmax = 55 nm (∆ E max=33 nm) as

they have got absorption (emission) values at (33c); λmax=543 nm; εmax=15830 M-

1cm-1 (33c; E max=620 nm (56 kcal/mol)). This is due to the decrease extended

conjugation in quinolin-2-ium than quinolin-4-ium as electron sink. It was obvious that

dyes (32, 33 a-c) have further stock shift between the fluorescence (emission)

spectra in 95% EtOH underwent change to higher & lower depending on alkyl

substituent & nature of heterocyclic quaternary salt. Thus, dyes (32, 33 a-c) showed

a range of Δ λ 55-81 nm concomitant with 54-61 x 105 kcal/mol kcal/mol respectively.

Such diffuse & large stokes shifts for (32, 33 a-c) was suggested to be partly result

of charge transfer (solute-solvent) interaction of such dyes, in addition to, stokes shift

effects the generation properties were explained by change in the mobility of π-

electron in conjugated chromophore of such dyes, Table (1). The excitation energy

(E0-0) of dyes depend basically on the type of substituents and the nature of

heterocyclic quaternary salt (A) which have a great effect on the number of π-

conjugations in fluorophore and calculated from the intersection of absorption



(emission) spectra, the first (lower) excitation energy (E0-0) of (32a; E0-0=2.33).

Substituting of A=H-4-ium in dye (32a) by A=C4H4-4-ium in dye (32b; E0-0=2.10)

causes lower in gap (E0-0). This is due to increasing conjugation in dye (32b) than

(32a). Substituting A=C4H4-4-ium in dye (32b) by A=C4H4-1-ium in dye (32c) resulted

in high E0-0 (32c; E0-0=2.21). This is due to decreasing conjugation in dye (32c) compared to (32b). Substituting of A=C4H4-4-ium in dye (32c) by A=C4H4-1-ium in

dye (33a) increasing E0-0 value (33a; E0-0=2.27). This is due to decreasing the

conjugation inside the dye molecule. Substituting A=H-4-ium in dye (33a) by

A=C4H4-4-ium in dye (33b) causes decrease in E0-0 value (33b; E0-0=2.01). This is

due to increasing conjugation. Substituting A=C4H4-4-ium in dye (33b) by A=C4H4-1-

ium in dye (33c) causes increase in E0-0 value (33c; E0-0=2.13). This is due to

decreasing conjugation in dye (33c) compared to dye (33b). On comparison of dyes

(29a-d & 30a, b & 32, 33 a-c), It was observed that, the absorption maximum of

(29a-d & 32, 33 a-c) are red-shifted that those of (30a, b) attributed that dyes (30a, b) possess only one [ICT] pathway compared to dyes (29a-d & 32, 33 a-c) which

have two [ICT] pathways. Table (1): Normalized Absorption and Emission Spectra of (25A, B & 26A,B, 29a-d, 30a, b & 32, 33 a-c) in (10-4 M) EtOH

Comp. No.

λmax (εmax)

Absorbed Colour

E max (nm) (Intensity

105)

Transmitted Colour

Stokes shift

I E0-0

25A 399

(2.1395)

_ 460 _ 61 425

(2.917)

25B 412

(0.1081)

Violet 530 Yellow- green 118 443

(2.798)

26A 401

(3.1810)


(2.837)

26B 422

(0.0937)


(2.931)

29a 493 (1.60)

Blue- green

568 (27)

Red 75 535 (2.31)

29b 483 (1.78)

Green-Blue 550 (28)

Orange 67 522 (2.37)

29c 536 (1.80)

Green 589 (26)

Red 53 560 (2.21)

29d 495 (1.98)

Blue- green

559 (30)

Red 64 542 (2.28)

30a 428 (1.00)

Violet 570 (60)

Yellow- green 142 499 (2.48)

30b 470 (1.07)

Blue 584 (55)

Yellow 114 515 (2.40)

32a 493 (1.25)

Blue- green

566 (60)

Red 73 530 (2.33)

32b 545 Green 626 Purple 81 589



(1.65) (54) (2.10) 32c 530

(0.672) Green 605

(54) Purple 75 560

(2.21) 33a 503

(1.20) Green 584

(55) Purple 81 546

(2.27) 33b 598

(1.64) Orange 653

(61) Green-blue 55 614

(2.01) 33c 543

(1.58) Green

620 (56)

Purple 77 582 (2.13)

Tables (1) Abbreviations

λmax (nm,), ε max (104 M-1cm-1,), Emax (nm,), (kcal/mol), I (nm, and E0-0 (eV, HOMO-

LUMO) calculated point of the experimental absorption (emission) spectra (EtOH).

The spectral behavior of (29a, d & 30b & 32c & 33a, c) in aqueous universal buffer

solution of different values of pH (2.5, 4.5, 5.5, 7, 8, 9.3, 10.6, 11.9) [28], Table (2)

showed that they absorbed fundamental blue colour light absorption, λmax = 360-400

nm and near violet light extended to green light λmax = 410-630 nm. Such dyes in

aqueous universal buffer solution reveal fundamental violet light absorption at

pH=2.5 with batho (hypso)-chromic shifted in fundamental blue light & blue-green

light absorption at pH≥7.0 relative to ethanol. The hypsochromic shift of fundamental

violet light absorption at pH = 2.5 due to protonation of electrons lone pair on the

nitrogen atom which represent electron source atom and so responsible for charge

transfer in such solution of low pH value & therefore the interaction is inhibited, & the

protonated form does not absorb energy in the visible region. On the other hand, the

resulted bathochromic shift as the pH of medium increases due to the fact that

protonated compound becomes deprotonated & molecule mesomeric rest interaction

becomes high consequently the CT interaction within free base is facilitated. The

spectral behaviour of (29a, d) in aqueous universal buffer solution absorbed

fundamental violet extended to blue green light absorption of (29a, λmax = 407-499

nm] absorbed fundamental violet light extended to green light for (29d, λmax = 422-

510 nm]. In acid (pH ≥ 2.5) medium such dyes undergo a hypsochromic colour shift

due to protonation of nitrogen electrons lone pair in pyridine ring cases

intramolecular charge transfer (CT) between heterocyclic donor (oxygen) and

heterocyclic acceptor nitrogen atoms does not occur, and long wave length CT band

disappears. On the other hand, the resulted bathochromic shift as pH of medium

increases is due to that protonated compounds become deprotonated and their

molecule mesomeric interaction rest becomes high and consequently CT interaction



with free base is facilitated. On comparison of absorption spectra in aqueous

universal buffer solution of (29a, d), it was obvious that dye (29d) has got absorption

as it absorb fundamental blue green light absorption for (29d, λmax = 422-510 nm,

pka=2.4, 7.8) values which bathochromically shifted by (∆λmax = 11nm) with respect

to (29a, λmax = 407-499 nm, pka=8.1, 8.9) due to more extended conjugated

chromophore in (29d) from the electrons lone pair of pyridine ring nitrogen as

electron source towards pyridin(quinolin)-[(4)1]-ium salt as electron sink. It was

obvious from pka values that dye (29d) was possible to be used as a photosensitizer

in acidic and basic media, Table (2 & 3). The spectral behavior of (30b, 32c & 33a, c) in aqueous universal buffer solution showed that such dyes absorbed fundamental

violet light absorption light extended to green blue for (30b, λmax = 431-489 nm),

absorbed fundamental violet light extended to green absorption for (32c, 33a, 33c,

λmax = 420-550 nm). In acid (pH ≥ 2.5) medium such dyes undergo a hypsochromic

colour change due to protonation pyridine ring nitrogen atom electrons lone pair. In

such cases the intramolecular charge transfer (CT) between heterocyclic donor

(oxygen) & heterocyclic acceptor nitrogen atoms does not occur & the long wave

length CT band disappears. On the other hand, the resulted bathochromic shift as

pH of medium increases due to protonated compounds become deprotonated & their

molecule mesomeric interaction rest becomes high & consequently CT interaction

with free base is facilitated. On comparison of absorption spectra of (30b, 32c, 33a, 33c) in aqueous universal buffer solution, it was obvious that (33c) has got

absorption fundamental violet light absorption in acidic medium and extended to

green in basic media for (33c, λmax = 458-545 nm, pka=4.1, 11.9) & might be used as

photosensitizers in both acidic & basic medium with bathochromically shifted for

(30b, 32c, 33a, ∆λmax = 56, 4, 36 nm) with respect to (30b, λmax = 431-489 nm,

pka=10 (32c, λmax = 409-541 nm, pka=6.5, 8.2, 8.7), (33a, λmax = 426-509 nm,

pka=8.1, 9.1] due to more extended conjugation chromophore in dye (33c) from

pyridine or pyrazole heterocycle nitrogen atom electrons lone pair in spiro pyrazolo

[3,4-b] pyridin-4,9'-xanthen]skeleton supplemented by hyperconjgated from methyl

as electron source towards pyridin(quinolin)-[(4)1]-ium salt as electron sink, Tables (2 & 3). On comparison of all selected self-assembly [ICT] heterocycles & related

methine cyanine dyes. It was obvious that (29d, 32c, 32b, 33a, 33c) have high

fundamental absorption & bathochromically shifted as absorbing fundamental red



light at (λmax = 500-650) in the order (33c >32c > 32b > 30b > 29d > 33a) which

absorb fundamental green blue light at (λmax = 430-499) in the order (29a>30b. It

was concluded that (29a, d, 30b & 33a, c) having covalent hydration or appearance

of absorption band in low ph. Thus, it was obvious that the acidic-ethanol solution of

such dyes gives a permanent colour (deepening in colour) & discharge on

basification due to suggested covalent hydration phenomenon. Such phenomenon

was occurred in aqueous media, thus heterocyclic moieties changed into

corresponding cations & covalent hydrated in acidic media. Table (2): Absorption (nm) & Extinction Coefficients (104 mol-1cm- 1) of (29a, d, 30b, 32c & 33a, c) in Universal Buffer Solution.

Table (3): Characteristic Absorbance λmax for (29a,d,30b,32c & 33a,c) in Universal Buffer Solutions

Dye λmax pH

Absorbance 29a λ445

29d λ452

30b λ 430

32c λ 470

33a λ430

33c λ498

2.5 0.354 1.916 0.342 1.123 1.798 0.426

4.5 0.926 2.458 0.271 1.292 1.862 0.657

5.5 0.65 2.47 0.172 1.185 2.066 -

7 0.828 1.408 0.49 0.858 1.676 0.727

8 0.612 1.831 0.351 1.06 1.825 0.617

9.3 0.738 2.486 0.722 - 2.834 0.739

10.6 0.661 2.619 1.186 0.896 - 0.467

11.9 - - 0.768 - -

Comp.

No.

Universal buffer

Color Abs. range (Trans.)

2.5 4.5 5.5 7 8 9.3 10.6 11.9 λmax (εmax)

λmax (εmax)

λmax (εmax)

λmax (εmax)

λmax (εmax)

λmax (εmax)

λmax (εmax)

λmax (εmax)

29a 407 (1.56)

463 (1.73)

464 (1.88)

466 (1.96)

476 (1.96)

480 (1.96)

492 (1.96)

499 (1.96)

Violet to Green-Blue

(orange) 29d 422

(1.45) 449

(1.86) 466

(1.91) 486

(1.94) 491

(1.96) 497

(1.99) 501

(2.01) 510

(2.03) Blue- green

(Red) 30b 431

(1.26) 456

(0.93) 464

(0.98) 472

(0.95) 478

(0.98) 480

(0.99) 483

(1.02) 489 (1.c)

Violet to Green-Blue

(orange) 32c 409

(0.77) 430

(1.71) 454

(1.59) 505

(1.69) 526

(1.67) 534

(1.69) 539

(1.69) 541

(1.67) Violet to Green

(Purple) 33a 426

(1.33) 459

(1.02) 469

(0.92) 474

(1.07) 485

(1.08) 491

(1.08) 506

(1.06) 509

(1.10) Violet to Green

(Purple) 33c 458

(1.41) 476

(1.42) 523

(1.75) 525

(1.96) 526

(1.91) 539

(1.06) 545

(1.29) _ Violet to Green

(Purple)



pKa

8.1

8.9

-

2.4

7.8

8.8

10.1

6.5

8.2

8.7

8.1

9.1

-

4.1

11.9

-

EXPERIMENTAL

Melting points were uncorrected & determined using SMP-10 Melting point

apparatus (stuart make). 1HNMR spectra were recorded using a Bruker advance 400

MHZ using DMSO-d6 as solvent & TMS as an internal standard. FTIR spectra were

run using Bruker alpha spectrophotometer. Mass spectra were recorded in thermo

scientific Exactive (Esims). UV-Vis & fluorescence spectra were recorded using

SPECORD S600 & Horiba Fluromax-4 Spectrophotometers. 4-Formyl-3-methyl-1-

phenyl-pyrazolin-5-one (1) & 3-methyl-1-phenyl-pyrazolin-5-imine-4-keto methylene-

N-pyridin (quinolin)-4-ium iodide) (27a, b) were prepared in a way that described in

prospective references [22; 23, 29, 30]. Synthesis of 4-(3, 5-Dimethyl-1, 7-Diphenyl-1,4,7,8-Tetra[H]Bis-Pyrazolo[3, 4-b:4', 3'-e] Pyridin-4-yl)-[Pyrido[2, 3-d:6, 5-d']Bis-Pyrimidine] (25, 26)A An ethanolic solution of 3-methyl-5-oxo-1-phenyl-4,5-di[H]-1H-pyrazolin-4-

carboxaldehyde (1m mol) & 3-methyl-1-phenyl-1H-pyrazolin-5-one (2 m mol) and/or

barbituric acid in presence aqueous solution of oxalic acid was refluxed overnight at

115 °C. The reaction mixture was allowed to cool, quenched by adding 50ml of

distilled water & extracted by chloroform. The organic layer condensed & crystallized

from petroleum ether to give (25, 26) A. (25A): m.p. 135, Yield, 71, colour, red, Mol.

Formula,.C31H27N7O, M. Wt. (514), elemental analysis Calc. (Found) %, C, 72.50

(71.01), H, 5.30 (5.27), N, 19.09 (19.12), (25B): m.p. 145, Yield, 42, colour, reddish

brown, Mol. Formula. C31H25N7O, M. Wt. (512), elemental analysis Calc. (Found) %,

C, 72.78 (72.79), H, 4.93 (4.92), N, 19.17 (19.20)

Synthesis of 4-(3, 5-Dimethyl-1, 7-Diphenyl-Bis-Pyrazolo [3, 4-b: 4', 3'-e] pyridin-4(1H, 7H, 8H)-pyrido [2, 3-d:6, 5-d'] Dipyrimidine Self-Assembly Endo Cyclic [ICT] Functional Mero Cyanine Dyes (25, 26)B Fusion of (25, 26)A in piperidine catalyst (2-3 drops) for 30min. then 10ml of ethanol

added & refluxed for 3 hours. The reaction mixture allowed to cool & quenched by

water then extracted by ethyl acetate. The organic layer concentrated & crystallized

by hexane. (26A): m.p. 130, Yield, 62, colour, pale brown, Mol. Formula.

C19H15N7O5, M. Wt. (421), elemental analysis Calc. (Found) %, C, 54.16 (54.13), H,



3.59 (3.62), N, 23.27 (23.21). (26B): m.p. 165, Yield, 59, colour, red, Mol. Formula.

C19H13N7O5, M. Wt. (419), elemental analysis Calc. (Found) %, C, 54.42 (54.43), H,

3.12 (3.09), N, 23.38 (23.41)

Synthesis of 3, 6-Dimethyl-4-Oxo-1-Phenyl-4,7-Di[H]-1H-Pyr-azolo [3,4-b]Pyridin- Zero-5(4)-Methine Cyanine (28a, b) A mixture of (27a, b, 1 m mol) & excess of acetic anhydride was irradiated in

microwave oven for 9 minutes at 200 watts under solvent-free conditions. After

reaction completion, the reaction mixture was allowed to cool & poured on crushed

ice & then solid thus was separated collected by filtration &recrystallized from

ethanol. (28a): m.p. 165, Yield,59, colour brown, Mol. Formula.C21H21IN4O, M. Wt.

(472), elemental analysis Calc. (Found) %, C, 53.40 (53.67), H, 4.48 (4.50), N, 11.86

(11.81), (28b): m.p. 120, Yield,45, colour, pale brown, Mol. Formula. C25H23IN4O, M. Wt. (522), elemental analysis Calc.(Found) %, C, 57.48 (57.44), H, 4.44 (4.39), N,

10.73 (10.91)

Synthesis of 3-Methyl-1-Phenyl-1H-pyrazolo [3, 4-b] pyridin-(7H)-5-Zero[4(1)] Methine-4-Mono[2(4)]Methine Cyanine Dyes (29a-d) A mixture of (28a, b, 1mmol) and 2-methyl-pyridin(quinolin)-2(4)-ium-ethiodide salts

(1mmol) was irradiated in microwave oven for 8 minutes at 200 watt under solvent-

free conditions. After reaction completion, the mixture was allowed to cool & poured

on crushed ice, and then solid was separated, collected by filtration & recrystallized

from ethanol, Table (4). Table (4): Characterization Data for (29a-d).

Comp

No.

Nature of Product %Calcd (Found)

M.p.

°C

Yield %

Colour Mol. Formula (Mol.wt)

C H N

29a 175 85 Red

violet

C33H33I2N5

(753)

52.6

(52.48)

4.41

(4.38)

9.29

(9.22)

29b 100 79 Reddish C33H33I2N5

(753)

52.6

(52.59)

4.41

(4.39)

9.29

(9.33)

29c 170 93 Violet C37H35I2N5

(803)

55.31

(55.31)

4.39

(4.30)

8.72

(8.75)

29d 115 85 Red C33H33I2N5

(753)

52.6

(52.55)

4.41

(4.40)

9.29

(9.32)



Synthesis of 3', 6'-Dihydroxy-3, 6-Dimethyl-1-Phenyl-1, 7-Di[H] Spiro [Pyrazolo [3, 4-b] Pyridin-4, 9'-Xanthen]-Zero-5[4(1)] Methine Cyanine (30a, b) A mixture of (28a, b, 1mmol), resorcinol (2 mmol) and 8M sulfuric acid (3 drops)

were added and heated in sand bath to 180°C for 30 minutes, the solution cooled to

room temperature and poured on crushed ice and the solid thus separated was

collected by filtration and recrystallized from acetone, Table (5). Synthesis of 3', 6'-Dihydroxy-3, 6-Dimethyl-1-Phenyl-1, 7-di [H] Spiro[Pyrazolo[3,4-b]Pyridine-4,9'-Xanthen]-2-ium-Ethiodide-Zero-5[4(1)] Methine Cyanine (31a, b) A mixture of (30a, b, 1mmol) and ethyl iodide (1m mol) were heating at 60 °C in

water bath for 30 minutes then 20 ml of ethanol were added, and the mixture

refluxed for 2-3 hours, the solution cooled to room temperature and ethanol

evaporated under pressure then the compound precipitated by petroleum ether and

recrystallized from ethanol to form the pure crystals, Table (5). Synthesis of 3', 6'-Dihydroxy-3, 6-Dimethyl-1-Phenyl-1, 7-di[H] Spiro [Pyrazolo [3, 4-b]Pyridin-4, 9'-Xanthen]-N-Ethyl-Pyridin (Quinolin)-Zero(Mono)-5(4)[15(4(1))]Methine Cyanine Dyes (32, 33) a-c A mixture of (31a, b, 1 mmol) and pyridin (quinolin)-4(1)-ium-ethiodide salts (1 mmol)

were stirred in 30 ml of ethanol for 10 minutes then 2-3 drops of piperidine added.

The reaction mixture refluxed for 6 hours at 110°C. After the reaction completion, the

product quenched by water and extracted by chloroform. The combined organic

layers dried over anhydrous Na2SO4, and filtered. After removing the solvent by

rotavapor, the compound crystallized by hexane and recrystallized from ethanol,

Table (5).



Table (5): Characterization Data for (30, 31) a, b & (32, 33) a-c

Comp No.

Nature of Product Mol. Formula

(Mol.wt)

%Calcd (Found) C H N M.p.

°C Yield

% Colour

30a 160 61 Red brown

C33H29IN4O3 (656)

60.37 (60.33)

4.45 (4.42)

8.53 (8.51)

30b 165 78 Red C37H31IN4O3 (707)

62.89 (62.82)

4.42 (4.40)

7.93 (7.92)

31a 164 53 red C35H34I2N4O3 (812)

51.74 (51.70)

4.22 (4.20)

6.90 (6.94)

31b 172 67 violet C39H36I2N4O3 (862)

54.31 (54.34)

4.21 (4.25)

6.50 (6.94)

32a 175 53 red C43H45I2N5O3 (933)

55.32 (55.34)

4.86 (4.845

)

7.50 (7.64)

32b 235 60 violet C47H47I2N5O3 (983)

57.38 (57.40)

4.82 (4.72)

7.12 (7.26)

32c 228 59 violet C47H47I2N5O3 (983)

57.38 (57.33)

4.82 (4.81)

7.12 (7.16)

33a 254 61 violet C43H45I2N5O3 (933)

55.32 (55.32)

4.86 (4.845

)

7.50 (7.52)

33b 269 64 violet C47H47I2N5O3 (983)

57.38 (57.40)

4.82 (4.72)

7.12 (7.10)

33c 275 56 violet C47H47I2N5O3 (983)

57.38 (57.43)

4.82 (4.87)

7.12 (7.15)

ACID-BASE PROPERTIES

The organic solvents were used of spectroscopic grade which purified according to

the recommended methods [36]. The absorption spectra of dyes in organic solvents

were recorded within wavelength (350-700 nm) on UV/Visible recording using 1cm

cell in spectrophotometer. The stock solution of dye was of order 10-3 mol-1dm-3

solutions of low molarities used in spectral measurements were obtained by accurate

dilution PHYSICO-CHEMICAL WORKING SOLUTIONS STUDIES

A-For studying the effect of pure solvents in visible range, an accurate volume of

stock solution of dyes were diluted to appropriate volume in order to obtain required

concentration. The spectra were recorded immediately after mixing in order to

eliminate as much as possible the effect spectral of time. B- For studying the

behaviour in aqueous universal buffer solutions, an accurate volume of stock

solution was added to 5 ml of buffer solution in 10 ml measuring flask. The pH of



solution was checked then absorption spectra of dyes in different pH solutions were

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